FI90984C - Process for dry cationization of galactomannans - Google Patents

Description

i 90984

Method for dry cationization of galactomannans

The invention relates to a dry process for the preparation of cationic galactomannans by reacting galactomannans with alkylene epoxides in the presence of water in an alkaline solvent.

Galactomannans are an important group of plant hydrocolloids, present as reserve carbohydrates, as observed, especially in the seed protein of many legumes. However, only guarana (guar gum) and carubin (kernel meal of John’s breadfruit) have industrial significance in Kay-tannd. Guarana is found in the seed protein of guar beans (Cyamopsis tetragonoloba L.), which belong to the genus Palil-15 of the genus Papilionaceae. Guar is an old crop that is currently grown on a large scale, especially in India, Pakistan and Texas.

Guarana contains 64% mannose and 36% galactose. The mannose units linked by a beta- (1,4) -glycosidic bond form long, unbranched chains to which private galactose molecules are attached to the alpha (1,6) bonds. Follow the mannose! that myOs galactose occur in the form of pyranose. Guarane has an average molecular weight of 220,000. Guarana is soluble in cold water.

Native and modified galactomannans based on Guar and John's breadfruit kernel flour are currently used industrially in a wide variety of fields. Thus, for example, in the oil, textile, paper, food, pharmaceutical, cosmetics and finishing industries, as well as in lining and water treatment. In papermaking, native galactomannans have been known for many years as "Wet end Additive" to improve the strength of paper.

35 By modifying the properties of products, new products can be strengthened, or new products with completely new types of properties can be created.

2

In order to improve the inherent affinity of galactomannans for cellulose and thus to achieve better fine fiber retention, it is possible to galactomannan and cationize.

EP-A0146911 discloses a process for reacting 2,3-epoxypropyltrimethylammonium chloride in an alkaline aqueous medium at 52 ° C.

According to EP-A-0130946, this reaction is likewise carried out in an alkaline medium which, however, additionally contains sodium tetraborate and which is partially neutralized with acetic acid before the addition of the cationization reagent.

GB-PS 1 136 842 contains more detailed information on the products obtained by reacting 2,3-epoxypropyltrimethylammonium chloride with galactomannans in an alkaline aqueous medium.

According to these publications, the cationized product must be dried before further use, after which it must be ground and sieved.

It is an object of the invention to provide a process for the preparation of cationized galactomannans in which stirring energy is used for only a short time, and the cationized galactomannans can be further processed without further post-treatment (screening, drying, etc.).

The invention relates to a process for the dry cationization of galactomannans by reacting them with alkylene n-oxide oxides of the above formula Z * 1 CH - CH- (CH-) -N (I) so y tax 35 £> CH, -CH- (CH, ) _- N - R, IC- '(II) o xr3

II

90984 3 wherein n is 1, 2 tal 3, Rx, R2 and R3 are the same or different alkyl groups having 1 to 4 carbon atoms, or R2 is a benzyl group and X- is chloride, bromide, sulphate or acetate, in an alkaline water the process being characterized in that the reaction is carried out at a temperature of 5 to 60 ° C, the pulp being 0.1 to 3.0% by weight, based on galactomannan, of fine silicic acid and 0.5 to 8, 0% by weight, based on galactomannan (Atro), of alkaliates and / or aluminates or of a mixture containing alkali or alkaline earth metal hydroxides or oxides and alkali metal carbonates, respectively, or of a mixture containing one or more of these hydroxide and , oxides or carbonates with alkali silicate and / or aluminate.

The pH of the 15 N & a modified galactomannan is £ 9 (1% w / w solution).

For the preparation of cationic galactomannans according to the process of the invention, native or modified galactomannans or galactomannans-containing substances of arbitrary origin can be used. Native guar core flour is particularly preferably used.

According to the invention, the ether-terpine of galactomannans is carried out with alkylene epoxides of the general formula Z * 1 CH 2 -CH- (CH_) -N (I) 30 or preferably

R 1 <S> / n CH 2 -CH- (CH 2) n N 2 -R 2 X © (II) 35 \ J \ 0 x r 3 4 where n is a number from 1 to 3 and R 1 (R 2 and R 3 denote similar tal different alkyl groups having 1 to 4 carbon atoms, wherein Rx is benzyl and X * is chloride, bromide, sulfate and acetate 2,3-epoxypropyltrimethylammonium chloride is preferred.

An alternative to the process according to the invention is based on allowing the reaction with the abovementioned epoxides to take place when the mixture is 0.5 to 5% by weight of a compound corresponding to one of the following formulas: 10 ch3 CH - CH-CH- -N-CH, X ^ (III) 'and \

^ C2H5OH

15 ch3

Os' & or CH - CH-CHO-N-CH, OAcP (IV) i / 2 \ 0 C12H25 20 or CH - CH-CH -, - N-CH, X ^ (V)

V

25

These compounds are preferably used in admixture with epoxides of the formula (I) or (II) and may be present in the form of their chlorohydrins.

At most, the reaction medium then converts to epoxides of formulas (III) - (V) which react with galactomannans. Such mixtures are preferably prepared by preparing epoxides of formulas (I) and (II), as e.g.

U.S. Pat. No. 3,135,782 discloses the use of tertiary amines corresponding to the matrices of the epochs 90984 to form the compounds of formulas (III) to (V) described above.

However, in addition to the epoxides, the chlorohydrins can be prepared separately from myOs and mixed with the epoxides of the formula (I) in the proportions described above.

In general, it is appropriate to use about 0.005 to 0.5 moles of epoxide, preferably 0.5 to 0.30 moles of epoxide, per mole of galactomannan, based on glucose anhydride units (molecular weight 162.15) in the vehicle.

The specific surfaces of the spent silicasic silicas used are between 60 and 700 m2 / g, preferably between 15 100 and 450 m2 / g (BET measurement according to DIN 66131, N2 adsorption on liquid nitrogen), drying of the sample before heating 110 * C).

They are used in an amount of 0.1 to 3.0% by weight, preferably 1.0 to 2.0% by weight, based on galacto-20 mannan (absolutely dry).

Preferably, cellals are used in the form of hydrophilic, precipitated silicic acids having a specific surface area of from 190 to 450 m 2 / g, in particular spray-precipitated, precipitated silicic acid having a specific surface area of 190 m 2 / g.

According to the invention, the reaction mixture contains the alkali-active substance (s) mentioned in claims 1, in particular alkali metal methacylate and / or alkali aluminate, in an amount of from 0.5 to 8.0% by weight, in particular from 1.5 to 4.5% by weight, and 10 to 60% by weight, preferably 20 to 30% by weight, of water, all values being calculated from the bed of galactomannan used (absolutely dry).

Usable polyols are also mixtures of alkali or alkaline earth metal hydroxides and oxides and alkali metal carbonates. Mixtures of one or more of these oxyl-35s, hydroxides or carbonates with alkali silicate and / or aluminate are also suitable.

6

Alkali especially means sodium or potassium, alkaline earth especially calcium.

Sodium metasilate in particular is used as silicate.

In a particularly suitable embodiment, the ErSB uses the alkaline active substance (s) in the form of a powdered mixture with finely divided, hydrophilic silicic acid (hereinafter referred to as "activator").

The activator contains 10 to 50% by weight of silicic acid and 90 to 50% by weight of these substances.

According to the invention, the process is carried out in such a way that a mixture consisting of galactomannan, alkali-active substance (s), silicic acid and alkylene-epoxide, which is generally used in the form of an aqueous solution, is homogenized in a blender.

The epoxide solution is suitably finely divided, added to the galactomannan in question in a commercially available form having a water content of about 7-15% by weight, preferably by spraying.

The alkaline active substance (s) and silicic acid may be added before the galactomannan or its fraction.

The powdered activator is preferably mixed with galactomannan before the epoxide solution is added. The epoxy solution and the alkaline component can also be added simultaneously to the mixing unit.

The mixture obtained in connection with the preparation of 2-epoxide by reacting the corresponding halohydrin with alkaline active substances, such as, for example, alkali metal hydroxide, can be used if the alkali halide formed in the final product does not decompose in the final product (risk of corrosion). Tata is not washed or neutralized and can be used directly.

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90984 7

The cationization reaction can take place both in the mixing agate or after homogenization of the myOs elsewhere in the storage silo in the corresponding, transport-packed packaging.

5 If the reaction is to take place in a stirring unit, high yields of 40-60% are reached after 30-24 hours at 30-60 ° C.

In a preferred embodiment, the process is cultured by homogenizing the reaction mixture at 5-40 ° C in a power mixer for 10 seconds to 25 minutes, after which it is fired from the mixer and allowed to complete the catholic node reaction in the same pre-mixed storage. slllossa.

In this case, it is advantageous to work preferably in the range of the lamp, in which, at the end, eslm. Due to the variation of the environment due to the season, the room lamp of the modest warehouses prevails, i.e. 18 to 30 ° C, especially 20 to 25 ° C.

The catalytic galactomannans prepared according to the process of the invention are generally in the form of a henojakola, a wettable powder, and from this it is possible to use the reaction fraction directly.

The power mixers are extremely suitable. steam bath mixers with one or more therapeutic cycles for continuous use, in particular for wetting-mixing mixers, in particular for continuous use.

According to the invention, the reaction reactants are also unnecessary, since the reaction mixture is poured into a bulky mixing pack to fill the storage bridge and the reaction is allowed to take place in a woman.

The wax transition time in the mixing unit makes it possible to carry out the sloping boiler continuously at the same time, whereas according to the state of the art, due to the mixing times of the tank 8, only intermittent cationization was known and meaningful.

The cationic galactomannans prepared according to the invention are suitable for their petroleum, textile, chemical and refrigerant industries, as well as for use in lining and water purification.

The use of cationic galactomannans (mainly guar) in the paper industry proves to be particularly advantageous. In T & 116, they have a positive effect on puncture pressure, breaking length, storage stability, retention, sheeting and fiber distribution in papermaking.

Unlike native guar, cationic guar is more dispersible and sill # has a vShemma tendency to cause water separation difficulties on the wire. In addition, the pulp is easier to grind in the context of papermaking when cationic guar is added. Cationic guar is also suitable as a water separation aid and as a drying agent.

The following types of activator were used for cationization of guar (guarane).

Table 1 Activator mixtures 25 Type Composition (% by weight) PC- # 01 69.45% sodium metasilicate

30.55 «KS

30 (mouth-dried silicic acid: 190 m2 / g) PC- # 02 40.30% sodium metasilicate

24.25% calcium hydroxide 35.45 KS

ti 90984 9 PC- # 03 72.12% sodium aluminate

27.88% KS

PC # 04 33.14% sodium metasilicate 5 37.70% sodium aluminate

29.16% KS

PC # 05 43.44% sodium aluminate

22.97% calcium hydroxide 10 33.59% KS

In all examples, spray-dried, hydrophilic silicic acid with a specific surface area (BET) of 190 m 2 / g was used as silicic acid.

15

EXAMPLES

In each case, 1000 g (5.551 mol) of native guar flour (moisture content 10.0%, insoluble nitrogen content 0.477%) were mixed for 5 minutes with the strongly mentioned activator (plow mixer) and the reagent solution, each containing 210.42 g (corresponding to a theoretical DS value of 0.250) of 2,3-epoxypropyltrimethylammonium chloride was sprayed onto the mass of the stirrer in 3 minutes. After stirring for an additional 15 minutes, the reaction product was packed in polyethylene bags and analyzed after a storage period of four days. Stirring and storage took place at room temperature (20 eC). Yield and degree of substitution (DS) were determined from the washed product according to the Kjeldahl nitrogen determination method.

Washing solution: isopropanol / water (60:40% by weight).

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Table 2

Activator Reagent solution 5 No. Type MaarS MSfirS tode11.DS Yield 1 PC- # 01 46.89 g 472.66 g 0.1188 47.5% 2 PC- # 02 40.77 g 472.85 g 0.0710 28.4 % 10 3 PC- # 04 51.12 g 471.91 g 0.1064 42.6% 4 PC- # 05 48.96 g 473.25 g 0.1110 44.4% 5 PC- # 06 42.93 g 471.52 g 0.0785 31.4% Composition of the metasilicate used: 48 ± 1% SiO 2, 51.0 ± 1% Na 2 O,

Composition of aluminate: 52-55% Al 2 O 3, 37-39% Na 2 O.

I;

Claims (2)

90984 A process for the dry cationization of galactomannans by reacting them with alkylene epoxides of the above formula Z * 1 CH, -CH- (CH 2) -N (I) 10 or R, ο /, β CH - CH- (CH-) -N-R-yP (II) \ 2 # in \ 2 15 \ / \ ox r3 where n is 1, 2 tal 3, Rx, R2 and R1 are the same or different alkyl groups in which is 1 to 4 carbon atoms, or Rx is a benzyl group and X (_) is chloride, bromide, sulphate or acetate, in an alkaline medium with water 1SnnS, characterized in that the reaction is carried out at a temperature of 5 to 60 ° C, where 1SnnS is 0, 1 to 3.0% by weight, based on galactomannan, of fine silicic acid and 0.5 to 8.0% by weight, based on galactomannan (Atro), of 25 alkali silicates and / or aluminates or a mixture containing alkali or alkaline earth metal hydroxides or oxides and alkali carbonates, respectively, or a mixture containing one or more hydroxides, oxides or carbonates with alkali silicate and / or aluminate a. Process according to Claim 1, characterized in that the reaction mixture containing galactomannan is homogenized in a blender for 10 seconds to 25 minutes, after which the mixture is removed from the mixer and the reaction is allowed to complete in a pre-filled storage tank.